CN1086471C - Composite film moisture barrier for on-cell tester - Google Patents
Composite film moisture barrier for on-cell tester Download PDFInfo
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- CN1086471C CN1086471C CN96192246A CN96192246A CN1086471C CN 1086471 C CN1086471 C CN 1086471C CN 96192246 A CN96192246 A CN 96192246A CN 96192246 A CN96192246 A CN 96192246A CN 1086471 C CN1086471 C CN 1086471C
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- silicon nitride
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- battery
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- 230000004888 barrier function Effects 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title description 10
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 44
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 87
- 239000011159 matrix material Substances 0.000 claims description 64
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 47
- 230000003287 optical effect Effects 0.000 claims description 23
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- 238000000151 deposition Methods 0.000 claims description 5
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- FEKJRSSKHNBSFT-UHFFFAOYSA-N 2-fluoro-1,3-dioxole Chemical compound FC1OC=CO1 FEKJRSSKHNBSFT-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 claims description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 4
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- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001552 radio frequency sputter deposition Methods 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
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- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
- H01M10/488—Cells or batteries combined with indicating means for external visualization of the condition, e.g. by change of colour or of light density
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/598—Guarantee labels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
- H01M6/5044—Cells or batteries structurally combined with cell condition indicating means
- H01M6/505—Cells combined with indicating means for external visualization of the condition, e.g. by change of colour or of light intensity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
- Y10T428/31544—Addition polymer is perhalogenated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
A light transparent moisture barrier useful for preventing moisture from destroying the effectiveness of a moisture sensitive cell condition tester on an electrochemical cell, comprises a plurality of very thin layers of amorphous silicon nitride and a hydrophobic fluorocarbon polymer on a flexible, polymeric substrate. The layers are formed on the substrate by a deposition process such as sputtering. The thickness of any individual layer is less than one micron.
Description
Background of the present invention
The field of the invention
The present invention relates to a kind of damp-proof membrane compound of optical transparency.More particularly, the present invention relates to a kind of optical transparency, film composite that can be used as the moisture barrier of (on-cell) tester on the quick battery that wets, it comprises silicon nitride layer and fluorocarbon polymer layer, also relates to the preparation method of described moisture barrier and has the wet quick on-cell tester and the electrochemical cell of described moisture barrier.
Background technology
Use condition tester for battery such as thermochromism potential tester to come to have become very common, and this has brought value-added benefit for battery fabricator and consumer from the state that visually shows the electrochemical cell that is commonly referred to as battery.These testers use with primary electrochemical cells, but as need them also can be used for testing the state of secondary or rechargeable electrochemical cell by the consumer.Using the most general tester at present is the thermochromic material that contacts with resistive element, and described off-color material constitutes the unitary member of battery packages, and wherein battery is an alkaline primary battery.The user places the electrode of battery between the contact of tester, and the extruding tester tip side with make it with battery electrode be that the battery end electrically contacts.The resistive element of tester is heated with cell voltage with being directly proportional, and thermochromic material shows that qualitatively its scope shows the battery status of " well " or " replacing ".For example at United States Patent (USP) 4,723, such tester is disclosed in 656.At United States Patent (USP) 5,188, integrated, thermochromism shell tester is disclosed in 231, this tester can take out from shell.Recently the battery status display is an integral part of battery label in the on-cell tester of exploitation.These on-cell testers comprise thermochromism type and new electrochemical type tester.Tester example is disclosed among the open No.0523901 A1 of European patent on the thermochromism type cell, and the disclosure content is introduced for reference here.The thermochromism type adopts resistive element to produce heat, thereby it can not be connected muchly on the electrode of battery and not make its continuous discharge, different with this thermochromism type, new electrochemical type is projected current from battery not, thereby it can be connected muchly on the electrode of battery and does not make battery discharge.This novel test device is disclosed in United States Patent (USP) 5,250, and in 905 and 5,339,024, the disclosure content is introduced for reference here.As at United States Patent (USP) 5, disclosed in 355,089, the state verification device adopts moisture absorption or in other words wet quick electrolyte composition on the battery of some electrochemical type, and need prevent that moisture from contacting electrolytical device, because this contact can damage the validity of tester.This patent disclosure the many methods that address this problem, wherein best is mica.But,, can not get can making it to be rolled into the long ribbon shape of mica volume or the mica of other shape, and economically viable commercial production method needs this mica volume though mica is more cheap.
General introduction of the present invention
The present invention relates to can be used as the optical transparency compound of moisture barrier, it comprises one deck silicon nitride and one deck fluorocarbon polymer at least at least, preferably two-layer at least silicon nitride and two-layer at least fluorocarbon polymer, and by deposit on matrix or form described silicon nitride and described fluorocarbon polymer layer forms described compound.In one embodiment, compound of the present invention comprises at least four layers, in a side of matrix one deck silicon nitride and one deck fluorocarbon polymer is at least at least arranged, and at the opposite side of matrix one deck silicon nitride and one deck fluorine carbon compound is at least at least arranged.In another embodiment, only on side of matrix or surface, have more than the silicon nitride of one deck with more than the fluorocarbon polymer of one deck.In the embodiment that has each more than the silicon nitride of one deck and fluorocarbon polymer on this embodiment and each opposite flank (as top and bottom) at matrix, this compound comprises silicon nitride and fluorocarbon polymer layer alternately.The present invention includes layered composite, each is wherein arranged more than two-layer silicon nitride and fluorocarbon polymer, the actual number of layer depends on the performance that this compound is required and only is subjected to the restriction of the ability of a large amount of numbers of plies of operator's deposit.In one embodiment, compound wherein of the present invention is as the moisture barrier of the on-cell tester of electrochemical cell, matrix is a flexible polymer, and this compound is film composite flexible, optical transparency, and wherein the thickness of each silicon nitride and fluorocarbon polymer layer is lower than 1 micron.In another embodiment, compound of the present invention is as the transparent packaging material of humidity-sensitive material and utensil.When being used as the moisture barrier of on-cell tester, but the optical transparency of compound makes user's observation measurer be used to refer to the color of battery status, mark or the shown battery status of other visual means.On-cell tester is meant the tester with the Visual Display battery status, and this tester by battery label or other approach muchly attached on the battery, but the present invention is not limited in this embodiment.Can use wet quick, the on-cell tester of a class of moisture barrier compound of the present invention is the tester that comprises at least a hygroscopic material, if described hygroscopic material has absorbed water vapor, will damage or the validity of damage test device.Another kind of tester comprises at least a component of water to play a role that need have scheduled volume, thereby it needs moisture barrier to keep the quantity of water in the tester.
Silicon nitride and fluorocarbon polymer all are water-insoluble, and the vapor permeability of selected fluorocarbon polymer is low as much as possible for moisture barrier is used.Use for moisture barrier, preferred fluorocarbon polymer is hydrophobic.The method for preparing layered composite is included in deposit one deck silicon nitride on the matrix, then deposit fluorocarbon polymer layer on silicon nitride layer.If desired more than the silicon nitride and the fluorocarbon polymer of one deck, proceed the alternating layer deposition process until having applied the required number of plies.Thereby, compound of the present invention is different with laminated material, the various layers that are pre-existing in are combined with each other by bonding or alternate manner in laminated material, and the alternating layer of compound of the present invention is to form on the spot on other layer of matrix and compound by deposit or painting method, described deposit or painting method comprise sputter, physical vapor deposition, and the latter comprises plasma fortified physical vapor deposition, chemical vapor deposition etc.
Brief Description Of Drawings
Fig. 1 illustrates according to 4 layers of moisture barrier on polymeric matrix of the present invention.
Fig. 2 (a) illustrates at the sectional drawing that has the on-cell tester on the battery of moisture barrier of the present invention, and Fig. 2 (b) illustrates the side view of the battery with on-cell tester and moisture barrier of the present invention with phantom view.
Describe in detail
Fig. 1 illustrates film moisture barrier 10 of the present invention, and it comprises flexiplast matrix 12, is deposited with silicon nitride layer on the both sides of this matrix, layer 14 and 16.Hydrophobic fluorocarbon polymer layer (layer 18 and 20) is deposited on each silicon nitride layer as shown in the figure.Thereby the multilayer moisture barrier shown in this figure is 4 layers of compound (not comprising matrix).As needs, these four layers of compounds can only be deposited on the side of matrix.The deposit alternate with each other on the both sides of side of matrix or matrix of additional silicon nitride and fluorocarbon polymer layer forms six, eight, ten, 12 or even 100 layers of compound as required.Like this, the ground floor silicon nitride deposition is on the one or both sides of matrix, and the ground floor fluorocarbon polymer is deposited on the silicon nitride layer then.Second layer silicon nitride deposition is on the ground floor fluorocarbon polymer then, and second layer fluorocarbon polymer is deposited on the second layer silicon nitride afterwards.Repeat this alternating layer deposition process has the required number of plies until formation film, layered composite.The thickness of each silicon nitride layer at about 200 dusts to the scope of about 5,000 dusts, preferred about 250 dust to 2500 dusts, more preferably 500 to 1,000 dusts.The thickness of each fluorocarbon polymer layer in the scope of about 250 dusts to 1 micron, preferred 300 to 5,000 dusts.The thickness that increases silicon nitride can increase the tendency that it breaks, and the thickness that increases fluorocarbon polymer layer then increases the stress of each illuvium, and this can increase the tendency that polymeric layer is peeled off from silicon nitride.On the other hand, reduce layer thickness and can increase the possibility that forms the space and not exclusively cover.Any of these situations all can reduce the validity of compound as moisture barrier.Certainly, the number of plies and layer thickness depend on the desired use of layered composite and depend on concrete fluorocarbon polymer.Moreover silicon nitride is more crisp, is easy to break when warpage or bending.Deposit polymeric layer or coating greatly reduce its tendency of breaking and also prevent its when operation breakage simultaneously on silicon nitride layer.In embodiment shown in Figure 1, all by adjacent polymeric layer protection, one of them is a fluorocarbon polymer for the both sides of silicon nitride layer or surface, and another kind is a matrix.Embodiment preferred is that silicon nitride surface is protected in the present invention's practice, and the skin of compound is a polymkeric substance.But as needs, the skin of compound can be a silicon nitride.
The present invention includes such embodiment, wherein (a) is not that all silicon nitride layers of compound all have identical thickness, (b) being not that all fluorocarbon polymer layer have identical thickness and (c) their combination, wherein is not that all equal thickness of silicon nitride layer is identical and be not that all equal thickness of fluorocarbon layer is identical.Other embodiment comprises a kind of compound, wherein be not all fluorocarbon polymer layer all by identical forming, have again, the some of them polymeric layer is not a fluorocarbon polymer.In a further embodiment, matrix 12 is fabrics with detachment surface of deposit ground floor thereon, makes layered composite break away from and with the form use of no matrix, and described compound forms on this matrix.In the another one embodiment, compound of the present invention forms on first matrix, and described first matrix is the fabric with detachment surface, this compound is transferred on second matrix and by any suitable approach to adhere to it then.Use for majority, the intensity of matrix needs to make layered composite can handle and use and not break in manufacture process.As mentioned above, transparent composite of the present invention can be used as the film moisture barrier of electro-chemical test device and can be used as the wrappage of wet quick food, chemicals, biomaterial and medicine, electronic equipment and goods.Except that the humidity resistance and the transparency to visible light, another advantage of compound of the present invention is the chemical inertness of silicon nitride and fluorocarbon polymer.Those skilled in the art can understand, and compound of the present invention also can design and be used for other purposes, comprise for example various parts of selective transmission and reflected electromagnetic spectrum of optical application.The difference of compound of the present invention and prior art compound is the combination of silicon nitride and fluorocarbon polymer, be that in addition silicon nitride layer and fluorocarbon polymer layer form by deposition process, rather than preform band shape or board-like material by bonding or alternate manner in conjunction with coming lamination to form layer structure.A but also within the scope of the invention following and formation one embodiment, promptly, of the present invention one or multi-disc compound lamination or be laminated on other compound or the material mutually, or their combination, form the laminar structure comprise a slice at least, preferred two or more compounds of the present invention.
By can be used for implementing silicon nitride layer that deposition process of the present invention forms be optical transparency and for amorphous.Silicon nitride also has good repellence and various corrosion environments is had good anti-corrosion moisture penetration except that optical transparency.As mentioned above, it is optical transparency and preferably hydrophobic can be used for implementing fluorocarbon polymer of the present invention.Can be used for implementing a kind of concrete fluorocarbon polymer of the present invention and comprise gang's optical transparency, amorphous polymer with excellent chemical resistance, they are by 2,2-bis trifluoromethyl-4,5-two fluoro-1,3-dioxole (PDD) and itself reaction form homopolymer or prepare as tetrafluoroethene (TFE), vinylidene fluoride, chlorotrifluoroethylene, fluorothene and perfluor (alkyl vinyl ether) reaction by PDD and other fluorochemical monomer.The multipolymer of commercially available PDD and TFE (wherein PDD is a principal monomer) is the Teflon AF that DuPont sells.Can be used for implementing the illustrative of other fluorocarbon polymer of the present invention but limiting examples comprises that the multipolymer of the teflon TEF that to be known PTFE, DuPont sell with Teflon FEP and hexafluoropropylene and DuPont are with the TEF of Teflon PFA sale and the multipolymer of perfluor (alkyl vinyl ether).Be big when block some or all in these fluorocarbon polymers opaque for light, but they are optical transparencies under the used layer thickness of the present invention.
Can be used for implementing layer deposition process of the present invention and comprise various PVD methods for example sputter and evaporation.That can also use has plasma polymerization, monomer gas phase deposit, various chemical vapor deposition, low-pressure chemical vapor phase deposition and a plasma fortified chemical gas-phase deposition method, and they are known in those skilled in the art.High speed method to matrix applying coating on cylinder or reel or stratiform thing also is known, and it for example is disclosed in the United States Patent (USP) 4,543,275 and 5,032,461.In general, deposit one deck only at every turn in vacuum chamber.Like this, deposit one deck silicon nitride on the one or both sides of matrix.Then will the target material in vacuum chamber change the matrix that fluorocarbon polymer maybe will apply silicon nitride into and transfer in another chamber, target material wherein is a fluorocarbon polymer.Deposit fluorocarbon polymer on silicon nitride layer then.Yet as need, can be in a vacuum chamber by at least two kinds of deposit sputtering targets of this indoor employing at the deposit of the one or both sides of matrix one deck silicon nitride and one deck fluorocarbon polymer at least at least.For example, carrying out in the vacuum chamber of layer deposit strengthening sputter by magnetron, under the situation of outgrowth one deck of matrix, matrix is an electrode, the target material of deposit be another electrode on matrix, is plasma between the electrode.In addition,, target material and plasma are arranged on the both sides of matrix for deposit one deck simultaneously once in both sides, in this case, at matrix or applied deposit one deck silicon nitride or fluorocarbon polymer on the both sides of matrix of silicon nitride.Have again, if matrix is the band or the film of motion, then by adopt the more than one target can be in the vacuum chamber order at matrix more than one material of deposit by time a time.Like this, if matrix is the band or the film of motion, when matrix motion during through first target or target group, setting this target for purposes of illustration is silicon nitride, just on the one or both sides of matrix deposit one deck silicon nitride.When the matrix that has applied silicon nitride continues to move to second target in the first target downstream chamber or target group, on silicon nitride layer with regard to deposit one deck fluorocarbon polymer, or the like.Like this, in vacuum chamber matrix can be on matrix during by one time coated with multiple layer forming compound as shown in Figure 1, or have compound than more or less number of plies shown in Figure 1.This method makes can suitable manufacturing expense produce relatively large compound of the present invention.
As mentioned above, United States Patent (USP) 5,250,905 and 5,339,024 disclose the on-cell tester that can contain one or more wet quick assembly, it thereby need divide the validity of infringement tester to prevent water with the moisture barrier that tester uses simultaneously, as disclosed such in the U.S. 5,355,089.Reach audience-proof a kind of method and be to use the little mica splitting that is arranged on the on-cell tester, and seal, as disclosed in the patent of ' 089 with suitable barrier material such as polyisobutylene.Be respectively the side view of the on-cell tester on the battery that has moisture barrier of the present invention and the top view of cut-away section shown in Fig. 2 (a) and 2 (b).Like this, Figure 2 shows that a kind of electrochemical cell 50, the on-cell tester 60 of the disclosed type of ' 089 patent that it has, and contain at least one hygroscopic part (not shown), tester is provided with film of the present invention, multilayer moisture barrier 10 and is sealed in the outside of metal battery container 52 by fluid sealant 62, and plastic label 70 coats batteries and also places on tester, sealing place and the moisture barrier.Tester 60 about 10 mil thick also are connected by unshowned mode on the positive pole 54 and negative pole 56 ends of battery.Contain for example a kind of polymer dielectric as disclosed tester 60 in the patent of ' 089, this electrolyte is contained in the 0.5M three fluosulfonic acid lithiums and poly-1 in the aprotic solvent (being ethylene carbonate and propylene carbonate), 1-difluoroethylene, this electrolyte are very moisture absorptions.Sealant material for example is maleic anhydride modified polybutylene elastic body, by at Piscataway, and the Huls of NJ, Inc. sells with Vestoplast V3645.Label is the PVC film that coats battery and moisture barrier/tester/fluid sealant, heat shrink then.Actual, for moisture barrier as the on-cell tester of electrochemical cell, label tester on the disclosed battery in the above-referenced patents for example, the gross thickness of moisture barrier is not more than about 1.5 mils, is preferably in about 1 mil or 25 microns.
The water infiltration of moisture barrier compound or moisture-vapor transmission are by following mensuration, promptly, the polymer dielectric band of 0.25 inch wide, 1 inch long and 3 mil thick is placed on the micarex of 1.5 mil thick, described polymer dielectric contains 0.5M trifluorosulfonimide lithium (lithium trifluorosulfonimide) salt and the 30wt% poly-vinylidene fluoride of 70wt% in the 3-methyl sulfolane.1 inch wide 1.7 inches long rectangle moisture barrier of the present invention is placed on this band, and the maleic anhydride modified polybutylene elastomeric seal glue by 2.5 mil thick is sealed in formation one laminate on the mica then, shown in Fig. 2 is overall.Like this, the hydroscopicity band is sealed between mica and the moisture barrier by fluid sealant.In the glove box of sealing, under anhydrous condition, finish this operation.The laminate that to so make keeps a week under 60 ℃ and 100% relative humidity then, shifts out the poly-vinylidene fluoride band that contains solvent and salt afterwards and analyzes its liquid water content by Karl Fischer titrimetry.Indication and the test method and the test condition that use among Here it is the following embodiment.
Can further understand the present invention with reference to following embodiment, wherein all moisture barriers all are optical transparencies.
Embodiment
Embodiment 1
In this embodiment, matrix is polynaphthenic acid ethyl (Kalodex) film of 1 mil thick, applies the thick silicon nitride layer of 500 dusts in each side of this matrix by silicon nitride target RF sputter in 1.5 milli torr argon atmosphers.Silicon nitride layer by this method deposit is an amorphous state.Afterwards, in 1.5 milli torr argon atmosphers, by RF magnetron sputtering apply 1500 dusts thick Teflon AF layer on every layer at two silicon nitride layers by Teflon AF target.By pointed determination of test method in the top detailed description, the per 24 hour time of the moisture-vapor transmission of the optical transparency of so making, film, multilayer moisture barrier is lower than 8 microgram water in the surface per square inch.
Embodiment 2
In this embodiment, matrix is polynaphthenic acid ethyl (Kalodex) film of 1 mil thick, with silicon nitride matrix is carried out sputter and apply in 1.5 milli torr argon atmosphers, only forms thick amorphous silicon nitride layer or the coating of about 500 dusts on a side of matrix.Sputter PTFE forms the thick PTFE layer of 1500 dusts on this silicon nitride layer then.Repeat this process once, form optical transparency, film, multilayer moisture barrier, it is included in alternately four layers of amorphous silicon nitride and PTFE (2 layers of silicon nitride and 2 layers of PTFE) on matrix one side, use the test method of embodiment 1, the moisture-vapor transmission of this moisture barrier is per 24 hours surface area 28 microgram water per square inch.
Comparative Examples A
It is similar to embodiment 1 that RF sputter in the argon atmospher of this experiment, polynaphthenic acid ethyl matrix and moisture see through test method.In this experiment, only in a side of matrix by SiO
2The target sputter applies the thick one deck monox of 500 dusts, applies the thick one deck PTFE of 500 dusts by the sputter of polytetrafluoroethylene (PTFE) target then on this layer monox.This process repeats twice, and alternating deposition silicon oxide layer and Teflon AF layer generate the optical transparency compound, and except that matrix, this compound comprises alternately six layers of SiO
xAnd PTFE (three layers of SiO
xWith three layers of PTFE), layer 6 or skin are PTFE.Use the test method of embodiment 1, so the moisture-vapor transmission of the optical transparency moisture barrier that forms is per 24 hours surperficial per square inch 250 microgram water.
Comparative example B
It is also similar to embodiment 1 that RF sputtering deposit, polynaphthenic acid ethyl matrix and moisture see through test method in the argon atmospher of this experiment.In this experiment, apply the thick one deck TiO of 150 dusts on the both sides of matrix film
2, the thick Teflon AF of deposit one deck 500 dusts makes compound as shown in Figure 1 above this layer.Use the test method of embodiment 1, so the moisture-vapor transmission of the optical transparency moisture barrier that forms is per 24 hours surperficial per square inch about 530 microgram water.
Comparative example C
It is also similar to embodiment 1 that RF sputtering deposit, polynaphthenic acid ethyl matrix and moisture see through test method in the argon atmospher of this experiment.In this experiment, the thick one deck ZrO of coating on both sides 200 dusts of matrix film
2, one deck Teflon AF that deposit 500 dusts are thick on this layer makes four layers of compound on matrix as shown in Figure 1.Use the test method of embodiment 1, so the moisture-vapor transmission of the optical transparency moisture barrier that forms is per 24 hours surperficial per square inch about 300 microgram water.
Comparative example D
It is also similar to embodiment 1 that RF sputtering deposit, polynaphthenic acid ethyl matrix and moisture see through test method in the argon atmospher of this experiment.In this experiment, apply the thick one deck Al of 500 dusts on the both sides of matrix film
2O
3, one deck (PTFE) that deposit 500 dusts are thick on this layer is made compound as shown in Figure 1.Use the test method of embodiment 1, so the moisture-vapor transmission of the optical transparency moisture barrier that forms is per 24 hours surperficial per square inch about 300 microgram water.
Comparative example E
It is similar to embodiment 1 that RF sputtering deposit, polynaphthenic acid ethyl matrix and moisture see through test method in the argon atmospher of this experiment.In this experiment, only on a side of matrix film, apply the thick one deck SiO of 500 dusts
x, one deck Teflon AF that deposit 500 dusts are thick on this layer.Repeating this process makes for twice and has alternately six layers (except that matrix) (three layers of SiO
xWith three layers of TeflonAF) compound, layer 6 or skin are Teflon AF.Use the test method of embodiment 1, so the moisture-vapor transmission of the optical transparency moisture barrier that forms is per 24 hours surperficial per square inch about 300 microgram water.
Comparative example F
This experiment is similar to comparative example D, and difference is to use Teflon AF to replace PTFE.Use the test method of embodiment 1, so the moisture-vapor transmission of the optical transparency moisture barrier that forms is per 24 hours surperficial per square inch about 300 microgram water.
Can understand, under the condition that does not depart from the above disclosed scope of the invention and essence, those skilled in the art may be obvious that and easily make enforcement various other embodiments of the present invention and improvement.Therefore, the scope of this paper appended claims should not be considered as being limited by the foregoing description, but claims should be interpreted as that covering is present in the feature of all novelties of can granting patent among the present invention, comprises that one of ordinary skill in the art of the present invention think all features and the embodiment of its equivalent.
Claims (5)
1. electrochemical cell, this battery has wet quick condition tester for battery and is used to make described tester moisture to be played the optical transparency moisture barrier of protective action, wherein said moisture barrier is included in a kind of compound on the polymeric matrix, described compound comprises the amorphous silicon nitride of one deck and one deck hydrophobic fluorine carbon polymer at least at least, their mutual alternating depositions, the thickness range of wherein said silicon nitride and fluorocarbon polymer layer is respectively 250 to 2,500 dusts and 250 dusts to 1 micron, and the thickness of wherein said moisture barrier is not more than 1.5 mils.
2. battery as claimed in claim 1, wherein said compound comprise two-layer at least described silicon nitride and two-layer at least described fluorocarbon polymer.
3. battery as claimed in claim 2 wherein is provided with a polymeric layer in the outside of described moisture barrier.
4. battery as claimed in claim 2, wherein said fluorocarbon polymer comprises at least a polymkeric substance that is selected from mainly in the group of being made up of following material: (i) PTFE, the (ii) multipolymer of TFE and hexafluoropropylene, the (iii) multipolymer of TFE and perfluor (alkyl vinyl ether), (iv) 2,2-bis trifluoromethyl-4,5-two fluoro-1,3-dioxole (PDD) be selected from mainly by PDD, TFE, vinylidene fluoride, chlorotrifluoroethylene, fluorothene, at least a monomer in the group that perfluor (alkyl vinyl ether) and their potpourri are formed reacts the polymkeric substance that is generated.
5. electrochemical cell according to claim 1, wherein said compound is a kind of optical transparency compound.
Applications Claiming Priority (2)
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| US08/376,700 | 1995-01-23 | ||
| US08/376,700 US5593794A (en) | 1995-01-23 | 1995-01-23 | Moisture barrier composite film of silicon nitride and fluorocarbon polymer and its use with an on-cell tester for an electrochemical cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1176696A CN1176696A (en) | 1998-03-18 |
| CN1086471C true CN1086471C (en) | 2002-06-19 |
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| CN96192246A Expired - Fee Related CN1086471C (en) | 1995-01-23 | 1996-01-22 | Composite film moisture barrier for on-cell tester |
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| US (2) | US5593794A (en) |
| EP (1) | EP0805977B1 (en) |
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- 1996-01-22 WO PCT/IB1996/000170 patent/WO1996023216A1/en not_active Application Discontinuation
- 1996-01-22 CN CN96192246A patent/CN1086471C/en not_active Expired - Fee Related
- 1996-01-22 AT AT96902414T patent/ATE423967T1/en not_active IP Right Cessation
- 1996-01-22 EP EP96902414A patent/EP0805977B1/en not_active Expired - Lifetime
- 1996-01-22 JP JP52275996A patent/JP4130223B2/en not_active Expired - Fee Related
- 1996-01-22 BR BR9606839A patent/BR9606839A/en not_active IP Right Cessation
- 1996-01-22 MX MX9705539A patent/MX9705539A/en unknown
- 1996-01-22 PL PL96321458A patent/PL182133B1/en unknown
- 1996-01-22 AU AU46743/96A patent/AU715557B2/en not_active Ceased
- 1996-01-22 CZ CZ972210A patent/CZ221097A3/en unknown
- 1996-01-22 DE DE69637843T patent/DE69637843D1/en not_active Expired - Lifetime
- 1996-01-22 NZ NZ301342A patent/NZ301342A/en unknown
- 1996-01-22 CA CA002210228A patent/CA2210228A1/en not_active Abandoned
- 1996-02-16 TW TW087207520U patent/TW358550U/en unknown
- 1996-08-05 US US08/695,277 patent/US5925479A/en not_active Expired - Lifetime
-
1997
- 1997-07-22 FI FI973088A patent/FI973088A/en unknown
- 1997-07-22 NO NO973380A patent/NO973380L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NZ301342A (en) | 1998-11-25 |
| US5925479A (en) | 1999-07-20 |
| ATE423967T1 (en) | 2009-03-15 |
| IL116640A (en) | 1999-12-22 |
| PL321458A1 (en) | 1997-12-08 |
| EP0805977B1 (en) | 2009-02-25 |
| NO973380L (en) | 1997-09-16 |
| BR9606839A (en) | 1998-05-26 |
| CN1176696A (en) | 1998-03-18 |
| EP0805977A4 (en) | 1999-08-04 |
| NO973380D0 (en) | 1997-07-22 |
| WO1996023216A1 (en) | 1996-08-01 |
| AR000730A1 (en) | 1997-08-06 |
| CZ221097A3 (en) | 1998-01-14 |
| JPH10512998A (en) | 1998-12-08 |
| AU4674396A (en) | 1996-08-14 |
| FI973088A0 (en) | 1997-07-22 |
| JP4130223B2 (en) | 2008-08-06 |
| CA2210228A1 (en) | 1996-08-01 |
| MX9705539A (en) | 1998-02-28 |
| FI973088A (en) | 1997-07-22 |
| EP0805977A1 (en) | 1997-11-12 |
| AU715557B2 (en) | 2000-02-03 |
| DE69637843D1 (en) | 2009-04-09 |
| TW358550U (en) | 1999-05-11 |
| PL182133B1 (en) | 2001-11-30 |
| US5593794A (en) | 1997-01-14 |
| IL116640A0 (en) | 1996-05-14 |
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Owner name: THE GILLETTE COMPANY Free format text: FORMER NAME OR ADDRESS: DURACELL CO., LTD. |
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Address after: Connecticut, USA Patentee after: Gillette Co. Address before: Connecticut, USA Patentee before: Duracell Inc. |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20020619 Termination date: 20110122 |